Nanoscale Donor-Acceptor Covalent Organic Frameworks for Mitochondria-Targeted Sonodynamic Therapy and Antitumor Immunity.

Sonodynamic therapy (SDT) based on O-dependent type II sonosensitizers (SSs) is limited by the hypoxic tumor microenvironment and aggregation-induced quenching (AIQ) of SSs. Type I SSs can generate reactive oxygen species (ROS) with reduced O dependence, but their efficacy is still constrained by the high electron-hole recombination rates and low ROS yields. Here, we report the synthesis of a novel two-dimensional nanoscale covalent organic framework (nCOF), Td-Pc, for mitochondria-targeted type I/II SDT.

Isostructural chiral metal-organic frameworks for enantioselective luminescence sensing of 1-phenyl-1,2-ethanediol.

We report the synthesis of isostructural chiral metal-organic frameworks (CMOFs), Zn-L-(Et), Zn-L-Me and Zn-L, based on Zn paddle-wheel secondary building units and three 1,1'-bi-2-naphthol (BINOL)-derived tetrabenzoate ligands [L-(Et), L-Me, and L], featuring different alkyl substituents at the 2,2'-hydroxyl positions. These CMOFs were evaluated as luminescent sensors for the enantiomers of 1-phenyl-1,2-ethanediol (PE). All three CMOF sensors exhibited selective quenching of -PE over -PE, with significantly higher quenching efficiencies than their corresponding free ligands.

A new type of CH binding site in a -bridging hexafluorosilicate ultramicroporous material that offers trace CH capture.

Hybrid ultramicroporous materials (HUMs) comprising hexafluorosilicate (SiF , SIFSIX) and their variants are promising physisorbents for trace acetylene (CH) capture and separation, where the inorganic anions serve as -bridging pillars. Herein, for the first time, we report a strategy of fluorine binding engineering in these HUMs switching the coordination mode of SIFSIX from traditional to rarely explored . The first example of a rigid HUM involving -bridging SIFSIX, SIFSIX-bidmb-Cu (bidmb = 1,4-bis(1-imidazolyl)-2,5-dimethylbenzene), is reported.

Homochiral BINOL-Based Metal-Organic Frameworks for Luminescence Sensing of Hydrobenzoin Enantiomers.

Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized.

Pore configuration control in hybrid azolate ultra-microporous frameworks for sieving propylene from propane.

Developing porous adsorbents for the complete sieving of propylene/propane mixtures represents an alternative method to energy-intensive cryogenic distillation processes. However, the similar physical properties of these molecules and the inherent trade-off among adsorption capacity, selectivity, diffusion kinetic and host-guest binding interactions in molecular sieving adsorbents makes their separation challenging. Here we report the separation of propylene/propane mixtures through a crystalline porous material (HAF-1) that features channels and shrinkage throats-the latter defined as narrower channels that connect the main channels and a molecular pocket-where the throat aperture is between the kinetic diameters of propylene and propane.

Cationic Metal-Organic Layer Delivers siRNAs to Overcome Radioresistance and Potentiate Cancer Radiotherapy.

Radiotherapy plays an important role in modern oncology, but its treatment efficacy is limited by the radioresistance of tumor cells. As a member of the inhibitor of apoptosis protein family, survivin plays a key role in developing radioresistance by mediating apoptosis evasion, promoting epithelial-mesenchymal transition, and modulating cell cycle dynamics. Efficient downregulation of survivin expression presents a promising strategy to enhance the antitumor effects of radiotherapy.

Exhaled Anesthetic Xenon Regeneration by Gas Separation Using a Metal-Organic Framework with Sorbent-Sorbate Induced-Fit.

Noble gas xenon (Xe) is an excellent anesthetic gas, but its rarity, high cost and constrained production prohibits wide use in medicine. Here, we have developed a closed-circuit anesthetic Xe recovery and reusage process with highly effective CO-specific adsorbent CUPMOF-5 that is promising to solve the anesthetic Xe supply problem. CUPMOF-5 possesses spacious cage cavities interconnected in four directions by confinement throat apertures of ~3.

Light and Guest Responsive Behavior in a Porous Coordination Network Enabled by Reversible [2+2] Photocycloaddition.

Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation.

Cross-Linking CdSO-Type Nets with Hexafluorosilicate Anions to Form an Ultramicroporous Material for Efficient CH/CO and CH/CH Separation.

A 4.6.8 topology hybrid ultramicroporous material (HUM), {[CuF(SiF)(L)]·G}, (L = 4,4'-bisimidazolylbiphenyl, G = guest molecules), 1, formed by cross-linking interpenetrated 3D four-connected CdSO-type nets with hexafluorosilicate anions is synthesized and evaluated in the context of gas sorption and separation herein.

Ultramicroporous Lonsdaleite Topology MOF with High Propane Uptake and Propane/Methane Selectivity for Propane Capture from Simulated Natural Gas.

Propane (CH) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are CH selective offer the potential to significantly reduce the energy footprint for capturing CH from natural gas, where CH is typically present as a minor component. Here we report the CH recovery performance of a previously unreported lonsdaleite, , topology MOF, a chiral metal-organic material, [Ni(-IEDC)(bipy)(SCN)], .

Switching Adsorbent Layered Material that Enables Stepwise Capture of C Aromatics via Single-Crystal-to-Single-Crystal Transformations.

Separation of the C aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C selectivity. Herein, we report the mixed-linker square lattice () coordination network [Zn(sba)(bis)]·DMF (, Hsba or = 4,4'-sulfonyldibenzoic acid, bis or = trans-4,4'-bis(1-imidazolyl)stilbene) and its C sorption properties.

Effect of Extra-Framework Anion Substitution on the Properties of a Chiral Crystalline Sponge.

Chiral metal-organic materials, CMOMs, are of interest as they can offer selective binding sites for chiral guests. Such binding sites can enable CMOMs to serve as chiral crystalline sponges (CCSs) to determine molecular structure and/or purify enantiomers. We recently reported on the chiral recognition properties of a homochiral cationic diamondoid, dia, network {[Ni(-IDEC)(bipy)(HO)][NO]} (-IDEC = -indoline-2-carboxylicate, bipy = 4,4'-bipyridine), .

Shape-Memory Effect Enabled by Ligand Substitution and CO Affinity in a Flexible SIFSIX Coordination Network.

We report that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. Specifically, whereas SIFSIX-23-Cu, [Cu(SiF )(L) ] , (L=1,4-bis(1-imidazolyl)benzene, SiF =SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX-23-Cu , [Cu(SiF )(L ) ] (L =2,5-bis(1-imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO . As-synthesized SIFSIX-23-Cu , α, transformed to less open, γ, and closed, β, phases during activation.

Crystal Engineering of a Chiral Crystalline Sponge That Enables Absolute Structure Determination and Enantiomeric Separation.

Chiral metal-organic materials (CMOMs), can offer molecular binding sites that mimic the enantioselectivity exhibited by biomolecules and are amenable to systematic fine-tuning of structure and properties. Herein, we report that the reaction of Ni(NO), -indoline-2-carboxylic acid (-IDECH), and 4,4'-bipyridine (bipy) afforded a homochiral cationic diamondoid, , network, [Ni(-IDEC)(bipy)(HO)][NO], . Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of adapted its pore structure to bind four guest molecules, 1-phenyl-1-butanol (1P1B), 4-phenyl-2-butanol (4P2B), 1-(4-methoxyphenyl)ethanol (MPE), and methyl mandelate (MM), making it an example of a chiral crystalline sponge (CCS).

A Robust Molecular Porous Material for C H /CO Separation.

A molecular porous material, MPM-2, comprised of cationic [Ni (AlF )(pzH) (H O) ] and anionic [Ni Al F (pzH) (H O) ] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year).

Black Titanium-Oxo Clusters with Ultralow Band Gaps and Enhanced Nonlinear Optical Performance.

A series of catecholate-functionalized titanium-oxo clusters (TOCs), to , with atomically precise structures were synthesized and characterized, including distinctive "boat" and "chair" conformations in and , respectively. These cluster compounds are prominent for their ultralow optical band gaps, as is visually evident from the rather unusual black TOCs (B-TOCs), to . The cluster structures were found to be ultrastable with respect to air, water, organic solvents, and even acidic or basic aqueous solutions in a wide pH range (pH 0-13), owing to the stabilizing effects of catecholate and its derivatives, as well as the carboxylate ligands.

Soil Microbial Resource Limitations and Community Assembly Along a Plantation Chronosequence.

Understanding soil microbial element limitation and its relation with the microbial community can help in elucidating the soil fertility status and improving nutrient management of planted forest ecosystems. The stand age of a planted forest determines the aboveground forest biomass and structure and underground microbial function and diversity. In this study, we investigated 30 plantations of distributed across the subtropical region of China that we classified into four stand ages (planted <9 years, 9-20 years, 21-60 years, and >60 years age).

Efficient propyne/propadiene separation by microporous crystalline physiadsorbents.

Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.

Reversible Switching between Nonporous and Porous Phases of a New SIFSIX Coordination Network Induced by a Flexible Linker Ligand.

Closed-to-open structural transformations in flexible coordination networks are of potential utility in gas storage and separation. Herein, we report the first example of a flexible SiF-pillared square grid material, [Cu(SiF)(L)] (L = 1,4-bis(1-imidazolyl)benzene), . exhibits reversible switching between nonporous () and several porous (, , , and ) phases triggered by exposure to N, CO, or HO.

Tuning the Gate-Opening Pressure in a Switching pcu Coordination Network, X-pcu-5-Zn, by Pillar-Ligand Substitution.

Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas-storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate-opening and gate-closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine-tune gate-opening and gate-closing pressure.

The electrochemical discrimination of pinene enantiomers by a cyclodextrin metal-organic framework.

Pinene is a family of bicyclic monoterpenes found in nature, which exhibits important applications in chemical industry and biomedicine; however, the discrimination methods used for pinene enantiomers are still rare. The alpha- and beta-pinene enantiomers were recognized and discriminated via an electrochemical method for the first time based on a cyclodextrin metal-organic framework (CD-MOF) as an electrochemical chiral sensor.